Roxarsone (3-nitro-4-hydroxy benzene arsenic acid) is an organoarsenic feed additive and has been widely used in the poultry industry to prevent coccidiosis and improve feed efficiency. The presence of roxarsone and its degradation products results in the instability of the anaerobic methanogenic process. This study investigated the degradation and speciation of roxarsone in an anaerobic granular sludge (AGS) system and the impacts of roxarsone and its degradation products on the structure of AGS. Roxarsone inhibited methane production, and the added roxarsone was rapidly degraded into 3-amino-4-hydroxyphenylarsonic acid (HAPA). After 240 days of incubation, the distribution of arsenic differed between the aqueous solution and the AGS in the assays of 20 and 350 mg/L roxarsone. Species analysis indicated that HAPA was completely degraded in all of the assays with roxarsone addition after 240 days of incubation. Species distribution was affected by the phases and the initial concentration of roxarsone added. The concentration of As(III) was higher than that of As(V) in both the aqueous solution and the AGS in all assays with roxarsone addition. The toxicity of roxarsone and its degradation products resulted in changes in the structure and the microorganism species in the AGS. (C) 2014 Elsevier B.V. All rights reserved.